Target and Nontarget Screening of PFAS in Biosolids, Composts, and Other Organic Waste Products for Land Application in France

Abstract

Zwitterionic, cationic, and anionic per- and polyfluoroalkyl substances (PFAS) are increasingly reported in terrestrial and aquatic environments, but their inputs to agricultural lands are not fully understood. Here, we characterized PFAS in 47 organic waste products (OWP) applied in agricultural fields of France, including historical and recent materials. Overall, 160 PFAS from 42 classes were detected from target screening and homologue-based nontarget screening. Target PFAS were low in agriculture-derived wastes such as pig slurry, poultry manure, or dairy cattle manure (median ∑46PFAS: 0.66 μg/kg dry matter). Higher PFAS levels were reported in urban and industrial wastes, paper mill sludge, sewage sludge, or residual household waste composts (median ∑46PFAS: 220 μg/kg). Historical municipal biosolids and composts (1976–1998) were dominated by perfluorooctanesulfonate (PFOS), N-ethyl perfluorooctanesulfonamido acetic acid (EtFOSAA), and cationic and zwitterionic electrochemical fluorination precursors to PFOS. Contemporaneous urban OWP (2009–2017) were rather dominated by zwitterionic fluorotelomers, which represented on average 55% of ∑160PFAS (max: 97%). The fluorotelomer sulfonamidopropyl betaines (X:2 FTSA-PrB, median: 110 μg/kg, max: 1300 μg/kg) were the emerging class with the highest occurrence and prevalence in contemporary urban OWP. They were also detected as early as 1985. The study informs for the first time that urban sludges and composts can be a significant repository of zwitterionic and cationic PFAS.

Volatility and Nonspecific van der Waals Interaction Properties of Per- and Polyfluoroalkyl Substances (PFAS): Evaluation Using Hexadecane/Air Partition Coefficients

“…To cope with the ever-increasing number of PFAS, many of which can be highly persistent, and avoid “regrettable substitutions”, it has been proposed that all PFAS should be regulated as a class. , However, individual PFAS have different molecular properties and different transport and distribution properties in the environment, and therefore varying ecotoxicological relevance. Even if a class approach is implemented, large amounts of PFAS have been produced and persist in many products, wastes, landfills, and the environment; − therefore, a greater understanding of the environmental fates and risks of individual PFAS is needed . Nevertheless, except for some acids of major concern and a few fluorotelomer alcohols, few experimental data describing the basic physicochemical properties of PFAS are available, which makes it difficult to perform reliable fate and risk assessments for diverse chemicals in the PFAS family.…”

Tracking PFAS in Drinking Water: A Review of Analytical Methods and Worldwide Occurrence Trends in Tap Water and Bottled Water

“…Signals lower than a set intensity threshold can also be discarded, and other types of filters may be applied (e.g., log-fold change with respect to blank). Peaks eluting at the same retention time (ΔRT< 0.1 min) should be checked to exclude adducts, dimers, and isotopes (potentially corresponding to the same entity) …”

“…Peaks eluting at the same retention time (ΔRT< 0.1 min) should be checked to exclude adducts, dimers, and isotopes (potentially corresponding to the same entity). 77 PFAS typically have low or negative mass defects because of the large number of fluorine atoms (Δm/z for each F = −0.0016). The mass defect range of PFAS is unique, and their decimal numbers have similar patterns (i.e., m/z for PFAS is very often XXX.9XXX or XXX.0XXX), resulting in CF 2normalized mass defects of 0−0.15 or 0.85−1 as discussed in Barzen-Hanson et al, and signals outside that characteristic PFAS mass defect range can thus be discarded.…”

Pharmaceuticals account for a significant proportion of the extractable organic fluorine in municipal wastewater treatment plant sludge

“…Full scan data (100-1500 Da; Rs=120 000 FWHM at m/z 200) were acquired using separate analyses in positive and negative mode. Thereafter, the acquired full scan data were interrogated for exact mass matches with 1214 suspects, which included 340 fluoropharmaceuticals, 3 424 fluoro-agrochemicals, 4 and 498 conventional PFAS (assembled from literature 19,[24][25][26][27][28][29][30][31][32][33] and presented in the SI -suspect lists). This search, which produced a total of 415 hits in positive mode and 309 hits in negative mode, was used to form an inclusion list for follow-up analysis in full scan (100-1500 m/z) data dependent MS2 mode (FS-ddMS2; Rs = 120 000 and 15 000 FWHM, respectively, both at 200 m/z), which facilitated collection of MS2 data when a measured exact mass matched a mass on the inclusion list.…”